Alkylation of hydrocarbons



chloride on a hydrocarbon material.

Patented Apr. 23,1946

Ernest W. Thiele, Chicago, Ill., assignor to Standard Oil Company, Chicago, 111., a corporation of Indiana Application July as, 1939, Serial No. 297,099

6 Claims. (01. zoo-683.4)

This invention relates to an improved process for the catalytic alkylation of isoparafiinswith olefins and relates more particularly to an improved alkylation process in which the catalyst. is a complex formed by the action of aluminum It is an object of this invention to provide an improved process wherein isopar'aflins are alkylated with oleflns in the presence of an aluminum chloride-hydrocarbon complex for the production of hydrocarbons suitable for fuel in automotive engines. Another object of this invention is to provide a process wherein mixtures of isoparaffins and oleflns are subjected to the. catalytic action of aluminum chloride-hydrocarbon'complex in order to form hydrocarbons of gasoline boiling range and higher, and in which a part or all of thehydrocarbons that could be suitably utilized in motor gasoline are recycled to the catalytic process as a part of the feed stock to make an aviation safety fuel. A still further object of this invention is to provide an improved alkylation process in which the feed stocks. are utilized to the greatest possible advantage for the production of hydrocarbons suitable for motor fuels, aviation fuels, etc. characterized by high octane numbers. Another object of this inven: tion is to provide a process for the production of aviation fuels, of ordinary boiling range, and for the production of an aviation safety fuel. Still further objects and advantages will become apparent as the description of my invention proceeds.

The accompanying drawing illustrates. schematically one preferred flow diagrainofasystem r cen-rare-out-mypfocess.

My preferred catalyst comprises a complex formed by the action of an aluminum halide, and preferably anhydrous aluminum chloride, on a hydrocarbon material, preferably in the presence of hydrogen chloride as a promoter. Although thewmplexform'ed bythe reaction of anhydrous aluminum chloride or aluminum bromide with olefins orwith aromatics may be used I prefer. to use the complex formed by the action of' aluminum chloride on parafilnic or naphthenic hydrocarbons or mixtures ofsuchhydrocarbons. It hasbeen discovered that acatalyst of greater activity, the effect of which on the reacting hydrocarbons can be more easily controlled,'is produced by the reaction of aluminum chlofideor aluminum bromide with a saturatedhydrocarbon than by the reactionof aluminum chloride or aluminum bromide with unsaturated hydrocar- 5 and claims the terms The exact nature of the complex is not known but it is believed that the saturated hydrocarbon does not replace one of the halogens nor does the I saturated hydrocarbon add to the aluminum halide in such a form that it can be recovered unchanged as may be done, for example, with the aluminum chloride-aromatic complex. A complex prepared from an aromatic-free light distillate from a Mid-Continent crude and anhydrous A1C13 gave the following analysis:

1 Weight per cen Aluminum 12.5 Chlorine 44 Carbon+hydrogen 43.5 Atomic ratio Cl/Al 2.7

In an effort to ascertain the chemical structure of this complex, a portion of it was carefully decomposed by adding water drop by drop with constant stirring, the' products being collected in a water reflux condenser, a solid carbon dioxideacetone tower, a gas absorption tube to remove HCl, and a permanent gas collector. The hydrocarbon layer was extracted with ether and the ether distilled from the hydrocarbon layer. The 45 volume per cent overhead from the distillation of the hydrocarbon istics:

Boiling range 142 F.-553 F. Refractive index N 13820-1537? The distillation revealed plateaus at 300 F. and

In addition the aluminum chloride treatment of a light naphtha, particularly a light naphtha of low antiknock properties, such as a. straight-run gasoline. will cause the .iscmeri'zation of at least a portion of the hydrocarbons present thereby producing branched-chain paramns desirable for use as an antlknock motor fuel and will also produce 'isobutane which, as will be pointed out later, is admirably for my'pr'ocess.

aluminum chloride-saturated hydrocarboncomplex, falumlnum chlohad the following charactersuited asv one of the reactants Throughout this specification April 23, 1946. E. w. THIELE ALKYLATION OF HYDROCARBONS Filed July 28, 1939 Thus, the alliyfnifofgasoliiie boiling buns The complex is withdrawn means of pump 19- anday xer 35. through valved line 50 if it is no longer suiliciently 1 -e'-.alkylation reaction, it may be"withdrawn' throughyalved line 5|. It maybe desirable to" rec ae a; portion of the complex which is not entirely' spent as to akylation with the least spent-tcatalystfrom the previous reaction in order that it maybe more fully utilized and to bleeda portionof it ofi through valved line 5| so that the volume of catalyst does not build up to anunwanted extent.

The alkymer and the unreacted hydrocarbons pass overhead from settler 41 through line 52 to mixer 53 where they are contacted with additional olefins from valved line 54 which joins line 32. Partially'spent v catalyst is-added to mixer 53 through valved line. 55-and the intermingled catalyst and hydrocarbons are-directed to reactor 56 throilg-h line 51. wherein conditions similar to those in reactor 39 are maintained. Temperature is controlled as in reactor 39 by fiuid which enters through line Ala and is discharged through line 42a. Thealkymer plus any unreacted' hydrocarbons together with the catalyst is withdrawn thrd l'gh-lineit and forced by pump 59 through valved line 69 to settler 6 I. A portion as in the previouslyjdescribed reaction may be re-.

cycled to the mixer .53 through valved line 62 aeeasoe paraillnacomiilelx "ttlestout and separates from valved line in while the' butane cut is withdrawn by pump 92 through line 83.. A portion is recycled through valved line 94 to fractionator'l'l to act as reflux in aiding'the separation of the I products in the fractionator if desired If there is present a considerable amount of'isobutane part or all of this may be returned to the process through valved line 95 which joins line 21. If the chief'constituent of the "Butane" cut is normal butane then this may be withdrawn through valved line 85 and used for blending with butane deficient motor fuels or as a fuel or directed to an lsomerization reactor (not shown) to convert the normal butanes'to isobutanes for use in the process.

The usual product from alkylation of isoparaffins, particularly the alkylation of isobutane with normally gaseous olefins, is a highly'branched paraflinic hydrocarbon having a very high octane number and, therefore, is particularly suitable for useas an aviationfuel or as a blending fuel for raising the octane number of motor fuels deficient inantidetonating characteristics. The product consists primarily of hydrocarbons having 6, '7 and 8 carbon atoms per. molcule upon the olefins used) although there may be present a certain amount of 9 and 10 carbon atom hydrocarbons. In place of the usual so-' called isooctane (2,2-4 trimethyl pentane) for aviation fuels it may be desirable to use a safety fuel. ,This-co'mprises a very high octane numwhich joins line n" stfl tler -fi V he yd ber'hydrocarbon having a higher boiling range carbons are again separated from the complex which is withdrawn through line 31 and directed to mixer by means of pump 63. A portion may also be recycled to mixer 53 through line 55.

.7M. ..eThealsyn-lerand'any remaining unreacted hydrocarbons pass from settler'Bl through line 64 to mixer 65. Olefins are added through line 92 while fresh aluminum chloride-complex is added through line 39 to mixer 65 wherein all streams are thoroughly agitated and directed to reactor 56 throughline '61. Again similar conditions of pressure and temperature are maintained, the

temperature control being regulated by fluid 5 which enters through line Mb and discharges through" line 62b.-- The react-ion product and the catalyst are withdrawn by means of pump 68 in line 69 and as before, a portion is returned to constitutes a somewhat greater danger to the aircraft.

In the course of my alkylation process it is quite possible that the alkylation reaction has proceeded beyond the simple alkylation of isobutane with the olefin-and that theoleflns have alkylated the alkymer which will, of course, conmixer 65 throughvalved line 10 if desired. The m t necessary ti te ti carbon at m remainder of the products in line 69 passes through valved line H to settler 12 wherein a separation between hydrocarbons and the catalyst is again made.

thr u h line." andiorced' y'fi p 14 to mixer a higher yield of safety fuel 53 through valvedline 55- A portion may also be recycled to mixer by line I5. Though three stages are shown, the actual number of stages may be more than three.

The alkmer plus any remaining unreacted hydrocarbons passesoverhead through line I5 to fractionator -'I'| equipped with bottom heating means 18. In fractionator 11 a separation is made between the normally gaseous hydrocaralkylated product heavier than gasoline. The gasoline cut may correspond to aviation or motor gasoline. The normally gaseous products pass The catalyst is wlthdliawn For this reason, there may be present hydrocarbons of higher boiling range than are suitable for aviation gasglinerbuttwhich-areadmirably suited -for'iise"as"anaviation safety fuel. To obtain the alkymer of low or intermediate boiling range may be recycled to the alkylation process for further'contact with the olefini'c feed. The alkymer of motor-fuel or aviation fuel gasoline boiling range is withdrawn to from fractionator 11 through line 89 and a part or all of it may be withdrawn for use as an avia-' tion fuel or motor fuel through valved line 99 and may, if desired; be blended with the isomerized naphtha from line 28. On the other hand range andJw i-a part or all of it may be directed through/val line 9l'*and-91f y pump 52 to mixer t5 wherein it is commingledwith the oIeFn ic gases from line 32 and with any unreacted olefinic gases from line fi i n edmth fresh aluminum chloridedrum -iwherein the separation is made between saturated hydrocarbon complex to alkylate furhydrocarbons having 4 carbon atoms per molecule and hydrocarbons having less than 4 carbon atoms per molecule and including anyhydrogen which may be present. The gases lighter than ther the a'ikymer. Alternatively, it may be retu jdtb mixer 53 through valved line 93 and valved line 94 which joins line 54 or to mixer 35 n "through valved line 95 which joins line 34. The the C4 hydrocarbons pass overhead through" proportion of alkymer of gasoline boilingrange (depending gas he succeeding reactor, and the alkymer withdrawn. This is most desirable methwithdrawn formotor or aviation fuel purposes and the amount withdrawn for further alkylation will depend entirely upon the relative amounts of aviation gasoline and aviation safety fue desired. 'I'he/safety fuel may *be'withdrawn gthrou'gh valved line 88. In the event that the safety fuel" alkymer contains alkymers too heavy for use in this connection, a further distillation may be made or the "safety fue alkymer of the desired boiling range may bewithdrawn as a side stream from fractionator H, the heavy bottoms being withdrawn for discard through line 88.

One advantage of this stepwise process lies in the control of the olefin to parafiin ratio of the reactants. There has been illustrated in my process a separation of reactants and'catalyst between steps, but it is possible to use a continuous process without intervening separation, the olefin stream being introduced at various points.

It is also possible to introduce fractionatorsbetween each of the steps to separate the complex, the alkymer and the unreacted gases, the complex being directed to the preceding reactor, the

0d of operation from an economic p I view, since the cost of the additional fractionation might be considered excessive.

This process illustrates an improved method of utilizing to the fullest extent the catalytic activity of my catalyst and the productionof-two desirable fuels particularly suited for aviation gasoline.

I claim: 1. In a countercurrent alkylation system which comprises a plurality of associated mixing, re-

acting and settling zones, the method of effecting the alkylation of iso-paraflinic hydrocarbons with olefinic hydrocarbons which comprises reacting a substantially aromatic-free naphtha with aluminum chloride to form a complex, introducing the complex into the mixer of. the last zone and thence passing it through the reactor of the last zone and settler of the last zone to the mixer, reactor and settler, respectively, of the preceding zone, introducing a mixture of isoparaflins and olefinic hydrocarbons first through the mixer, re-

actoi' andsettlerofthe preceding'zone and thence through the mixer, reactor and settler of the last zone, fractionating the hydrocarbons from the settler of the last zone into a motor gasoline fraction; an "aviation safety fuel and a lighter hydrocarbon fraction, respectively and -returning at least a part of said motor gasoline fraction to 7 one of said mixers.

2. The method of claim ,1 in which additional olefinic hydrocarbons are introduced .in succeeding stages.

3. Ina continuous process forthe production of aviation safety fuel by the alkylation of isoparaflinic hydrocarbons with normally gaseous olefl'nic hydrocarbons in the presence of analumi 1 num chloride-saturated hydrocarbon complex, the stepscomprising passing said isoparamnic hydrocarbons and said normally gaseous olefinic hydrocarbons to a first stage in'contact with par tially spent complex from at least one subsequent I stage under alkylating conditions, separately recovering treated hydrocarbons and spent complex from said first stage, passing said treated hydrocarbons and additional normally gaseous olefinic hydrocarbons to a subsequent stage in contact with an aluminum chloride-saturated hydrocarbon complex less spent than said complex in said first stage, said subsequent stage being maintained under alkylating conditions, separately recovering treated hydrocarbons and spent catalyst from said subsequent stage, directing said last-mentioned recovered complex to said first stage, fractionating said last-mentioned recovered treated hydrocarbons 'into an aviation safety fuel. fraction, a motor gasoline fraction, anda normally gaseous fraction, andreturning said motor gasoline fraction to said subsequent stage for alkylation toaviation safety fuel. Y

' 4. In a continuous process for the production of aviation safety fuel by the alkylation of iso- .paraflinic hydrocarbons with normally gaseous third stage for alkylationtoaviationsafety fuel;-

nic hydrocarbons in the presence of an aluminum chloride-satura e y rbonpomplex, the steps comprising passing said iso-paraifinic hydrocarbons and said normally gaseous olefinic hydrocarbons to a first stage in contact with partially'spenLcomplex from a second stage under alkylating conditions, separatelyfecovering treatride-saturated hydrocarbon complex under a1;

kylating conditions,aseparatelyiecovering treated hydrocarbons and spent complex from said third stage, directing said last-mentioned recovered .spent'complex to said second stage, fractionating said treated hydrocarbons from said third stage into an aviation safety fuel fraction, a motor gasoline fraction, and a normally gaseous fraction, andrecyclingsaid motor gasoline fraction to said 5. A process according to claim 4 in which said isoparaffinic hydrocarbon is isobutane.

6. A process according to claim 4 in which said isoparaflinic hydrocarbon is isobutane and said normally gaseous olefinic hydrocarbon is ethylene.

. ERNEST W. THIELE. 

